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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
8.1K
Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner-Sphere Reductive Elimination
Florian Ritter1, Lukas John1, Tobias Schindler1
1Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1A, 52074, Aachen, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 20, 2020
Summary
This study analyzes palladium-boron interactions in diphosphinoborane complexes. The findings reveal how borane acceptors stabilize palladium(0) and influence C-N coupling reactions.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
Background:
- Diphosphinoborane ligands (DPB) offer unique coordination properties.
- Understanding palladium-ligand interactions is crucial for catalysis.
Purpose of the Study:
- To investigate the dative Pd→B interaction in Pd(0) and Pd(II) complexes with DPB ligands.
- To elucidate the role of the borane acceptor in palladium stabilization and reactivity.
Main Methods:
- X-ray diffraction (XRD) for structural analysis.
- Boron-11 Nuclear Magnetic Resonance (¹¹B NMR) spectroscopy.
- Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) calculations.
- Density Functional Theory (DFT) modeling.
Main Results:
- The borane acceptor differentiates between Pd(II) and Pd(0) oxidation states, preferentially stabilizing Pd(0).
- Chemoselective C-N coupling was achieved using lithium amides with [(DPB)Pd(II)(aryl)I] complexes.
- DFT calculations showed minimal impact of Pd(II)→B coordination on reductive elimination rates.
Conclusions:
- The Pd→B interaction is sensitive to palladium oxidation state, favoring Pd(0) stabilization.
- DPB ligands facilitate chemoselective C-N coupling reactions.
- Inner-sphere reductive elimination is not significantly affected by Pd(II)→B coordination.
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